Aggregation behaviour of stereoregular poly(methyl methacrylates) in dilute solution: light scattering and proton n.m.r. study

The aggregation behaviour of syndiotactic and isotactic poly(methyl methacrylate) in methyl ethyl ketone, n-butyl acetate, and 2-ethoxyethanol was investigated by light scattering and ¹H n.m.r. spectroscopy. Syndiotactic poly(methyl methacrylate) remains in its molecular form in solution at temperatures above 60°–70°C; on cooling it undergoes aggregation followed by macroscopic separation (precipitation) of the polymer from solution. The rate of these processes depends on temperature, concentration of the polymer, and solvent. Molecular solutions of isotactic poly(methyl methacrylate) can be prepared only by long-term heating at temperatures above 100°–130°C. During cooling, isotactic macromolecules prior to separation form stable associates in the region limited by discrete temperatures, and below this region polymer precipitates. The individual stereo forms of poly(methyl methacrylate) are separated from solution at different temperatures which are above the θ-temperatures of the atactic polymer.     

Stereoregular poly(alkyl methacrylate)s: polymer-polymer and copolymer-polymer blends

Amorphous blends of isotactic and syndiotactic poly(methyl methacrylate) were found to be compatible. To evaluate the interaction between these tactic polymers, random copolymers of isotactic poly(methyl/ethyl methacrylate) were blended with syndiotactic poly(methyl methacrylate). Only the copolymers with an ethyl methacrylate content below 45% were compatible with syndiotactic poly(methyl methacrylate). Using a Flory-Huggins type treatment of copolymer mixtures, the segmental interaction parameters for poly(methyl methacrylate) with poly(ethyl methacrylate) and for isotactic with syndiotactic poly(methyl methacrylate) were calculated. The interaction parameter for the tactic poly(methyl methacrylate) pair was found to be small and negative.     

Characterization of two polypentadienes of differing tacticity by physical methods

The preparation of isotactic and syndiotactic 1,4-polypentadienes with a cis content of at least 70%–75% using i-Bu₂AlH/Ti(i-OPr)₄ and AlEtCl₂/thiophene/Co(acetylacetonate)₂ catalysts, respectively, is reported. Physical characterization of the vulcanizates, prepared by a common recipe, involving infrared analysis, DTA, simple stress–strain and swelling measurements, and dynamic mechanical measurements over a frequency range of 2 decades and temperature range of ?60°C to +20°C indicated that no isomerization had taken place during vulcanization and that stereoregularity of the polymer chains affected the resultant cure: the isotactic form was found to have a greater crosslink density than the syndiotactic form. Master curves covering an extended frequency range were constructed from the reduced dynamic mechanical data and the calculated quantities—thermal expansion coefficients of free volume and the fractional free volumes at the glass transition temperatures—agree with the accepted values. Glass transition temperatures of the isotactic and syndiotactic polymers are ?37°C and ?42°C, respectively, and for their vulcanizates, ?33°C and ?40°C, respectively.     

Matrix tacticity controlled tuning of microstructure,constitutive behavior and rheological percolation effect of melt‐mixed amino‐functionalized MWCNT/PP nanocomposites

Amino‐functionalized multi walled nanotube (MWCNT‐NH₂) filled isotactic PP and isotactic‐syndiotactic (70:30) mixed PP based melt‐mixed nanocomposites have been comparatively evaluated with regard to morphological, rheological and thermo‐mechanical properties. The ratio of mean free space lengths (L_f) to infiltrated mean free space lengths (L_inf) between nanotubes in isotactic‐syndiotactic (70:30) blended matrix based nanocomposites increased relatively indicating a dispersed‐morphology. The rheological percolation threshold increased up to a higher extent of MWCNT‐NH₂ loading (from ø_c ～ 2.3 × 10^?4 in isotactic to ø_c ～ 11 × 10^?4 in iso‐syndio blend) accompanied with the formation of a mechanically responsive network structure. van‐GurpPalmen plot showed a transition in the rheological response as a consequence of network morphology getting shifted to higher concentration of MWCNT‐NH₂ in the isotactic‐syndiotactic mixed PP based nanocomposites than in the isotactic based one. Constitutive modeling of complex viscosity response of the nanocomposites led to functional correlation between the percolation and relaxation dynamics of polymer chains. POLYM. ENG. SCI., 58:1115–1126, 2018. © 2017 Society of Plastics Engineers     

Measurement of the unperturbed dimensions of stereoregular poly(methyl methacrylate)

The results of measurements of unperturbed dimensions for a series of stereoregular poly(methyl methacrylates) are reported. The measurements were made by a recently developed method involving a gel permeation chromatograph coupled with an on-line low angle laser light scattering photometer. Measurements were performed in a thermodynamically good solvent, tetrahydrofuran at 25°C. The unperturbed dimensions were obtained by means of viscosity plots. Comparison of the results obtained by this method with those currently available in the literature, as well as with values predicted by statistical calculations, show good agreement. It was determined that a measurable difference occurs in the Mark-Houwink relationship between isotactic and syndiotactic poly(methyl methacrylate); isotactic poly(methyl methacrylate) is 30% more extended than syndiotactic poly(methyl methacrylate) in its unperturbed state; and isotactic poly(methyl methacrylate) exhibits a smaller degree of polymer solvent interaction than the syndiotactic form.     

Influence of the tacticity of poly(methyl methacrylate) on the miscibility with poly(vinyl chloride)

It can be concluded from the work of Schurer et al.¹⁰ that poly(vinyl chloride) (PVC) is more miscible with syndiotactic than with isotactic poly(methyl methacrylate) (PMMA). By choosing different molar masses for the various tactic forms of PMMA it is possible to obtain blends with PVC with similar phase behaviour, i.e. in all cases a cloud-point curve with a minimum in the vicinity of 190°C. In this way a more quantitative statement about the influence of the tacticity of PMMA on its miscibility with PVC can be made. One of the principal differences between syndiotactic or atactic PMMA and isotactic PMMA is the higher flexibility of the latter. Using Flory's equation of state theory it will be shown that the effect of this difference is large enough to explain the difference in phase behaviour observed. Heats of mixing of low molar mass analogues were also measured and found to be negative.     

Stereospecific anionic polymerization and copolymerization of 1,1-diphenylethyl methacrylate

1,1-Diphenylethyl methacrylate (DPEMA), which is a new methacrylic ester, was synthesized and polymerized by n-butyllithium (n-BuLi) in toluene and THF. The triad tacticity of the polymers was determined from the n.m.r. spectrum of poly(methyl methacrylate) (PMMA) which was derived from them. A highly stereoregular polymer was not formed either in toluene or in THF by n-BuLi between ?78° and 30°C. In toluene, the tacticity depended very much on the polymerization temperature, and unexpectedly, the polymer obtained at ?78°C was rich in syndiotacticity. The polymers obtained in THF were atactic regardless of the temperature. A highly isotactic polymer was formed with Grignard reagents. DPEMA (M₁) was also copolymerized with methyl methacrylate (MMA), diphenylmethyl methacrylate (DPMMA), and trityl methacrylate (TrMA) (M₂) in toluene and THF with n-BuLi; the tacticity of the copolymers was determined. Generally, the stereoregularity of the copolymers was lower than those of the M₂ homopolymers. In the copolymerization with MMA monomer reactivity ratios were also determined.     

Synthesis of stereoblock poly(methyl methacrylate) via transformation of isotactic-specific living polymer anion to syndiotactic-specific anion

Polymerization of methyl methacrylate (MMA) by isotactic poly(methyl methacrylate) (PMMA) living anion, prepared with t-C₄H₉MgBr in toluene at ?60°C, was carried out at ?78°C in the presence of trialkylaluminiums (R₃Al; R = CH₃, C₂H₅, and n-C₄H₉) to obtain a stereoblock PMMA, isotactic PMMA-block-syndiotactic PMMA. Among the R₃Als, (CH₃)₃Al gave most effectively the steroblock PMMA with narrow molecular weight distribution. The fraction of rr triad in the syndiotactic PMMA block increased with increase in the ratio of Al/Mg and reached about 76% at a ratio of Al/Mg ≥ 6. The method was also used to prepare stereoblock copolymer comprising isotactic PMMA block and syndiotactic block of butyl methacrylate. Stereocomplex formation and solution viscosity of the stereoblock PMMA were also studied.     

A comprehensive approach to the stereochemical and physical factors in nucleophilic substitution on PVC in the melt

The nucleophilic substitution reactin of poly(vinyl chloride) (PVC) with sodium benzenethiolate (NaBT) has been studied in the melt with the aim of determining whether a conformational mechanism is applicable under conditions that would apply in the polymer processing. The evolution of unreacted syndio, hetero, and isotactic triads content, and of the apparent molecular weight has been followed by ¹³C-NMR and GPC, respectively. The kinetic behavior was defined by choosing appropriate mixing conditions of temperature, shear stress, load, and amount of plasticizer. In all cases the kinetic curves attain a plateau after a rather fast reaction period has elapsed. The conversion at the plateau, that is, the reaction efficiency, proved to depend linearly on the amount of nucleophile and is hardly influenced by the mixing conditions for a given stoichiometric composition. The mixing conditions have been found to affect markedly the kinetics but to be quite inoperative on the evolution of both the content of unreacted tactic triads and the apparent molecular weight with degree of conversion. The results are discussed by taking into consideration those previously obtained in solution.     

Synthesis and characterization of poly(methyl methacrylate) nanoparticles by emulsifier‐free emulsion polymerization with a redox‐initiated system

In this study, the emulsifier‐free emulsion polymerization of methyl methacrylate (MMA) was initiated directly by a Cu²⁺/HSO redox system. Latex particles with negative charge due to the bonded anionic sulfite ion were successfully synthesized after 2 h of reaction at 40–60°C. Scanning electron microscopy pictures showed a uniform particle size distribution, and the average size decreased from 223 to 165 nm wit increasing reaction temperature from 40 to 60°C. The initiation step in the polymerization mechanism was proven to be a redox reaction, in which Cu²⁺ oxidized the bisulfite ion to produce an anionic sulfite radical and proton. The produced anionic sulfite radical then initiated the polymerization of MMA. Moreover, Cu²⁺ not only served as one component in the redox initiator system but also as a chain‐transfer agent that terminated growing polymer chains to produce chains with unsaturated end groups [poly(methyl methacrylate) (PMMA)? CH?CH₂]. For this system, about 17% PMMA? CH?CH₂ was produced. The tacticities of the PMMA latex prepared at 40–60°C were almost the same, about 62–64% syndiotactic, 33–35% heterotactic, and 3% isotactic. These PMMA latexes had almost the same glass‐transition temperature, 125–127°C, regardless of the reaction temperatures, and their weight‐average molecular weights were in the range between 254,000 and 315,000. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A novel method for preparing poly(alkyl methacrylates) and poly(methacrylic acids) of varying tacticity

In order to synthesize poly(methacrylic acid) and poly(alkyl methacrylates) over a wide range of polymer tacticity, the anionic polymerization of the following alkyl methacrylates (ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, n-hexyl, n-octyl, n-decyl, n-lauryl, and n-octadecyl) in toluene using phenylmagnesium bromide initiation was studied. It was found that the amount of isotactic polymer structure generally decreased as the size of the ester group increased. In all cases, the polymers had greater than 50% isotactic triad structure. Whether the polymerization was carried out at 0° or ?78°C had little or no effect on the tacticity of the polymer produced. It was found that the poly(alkyl methacrylates) produced could be hydrolyzed in concentrated sulfuric acid to poly(methacrylic acid). The poly(methacrylic acid) produced in the hydrolysis could be esterified with diazomethane to give poly(methyl methacrylate) or with diazoethane to give poly(ethyl methacrylate) with the same tacticity as the poly(alkyl methacrylate) from which the poly(methacrylic acid) was derived. It is possible, therefore, to produce poly(alkyl methacrylates) of a desired tacticity by polymerizing the appropriate monomer, hydrolyzing, and reesterifying the resultant poly(methacrylic acid) with a diazoalkane to give the desired poly(alkyl methacrylate).     

Low-frequency thermomechanical spectrometry of polymeric materials: Tactic poly(methyl methacrylates)

A computerized and automated torsional pendulum has been used to characterize amorphous poly(methyl methacrylates) at about 1 Hz in the temperature sequence 473° → 93° → 473°K. The effects of thermal prehistory, temperature cycling, water content, and tacticity are demonstrated. In particular, a comparison of the out-of-phase shear modulus (G″) versus temperature for “syndiotactic,” “atactic,” and “isotactic” polymer specimens shows that the intensity of the glassy-state β loss peak decreases with increasing isotactic content while the temperature of its location remains the same. Extrapolation suggests that completely isotactic polymer would not display a β loss peak. The shape and location of the G″ data at low temperatures indicate that the basic mechanism of the β process is the same for the three polymer samples and support the validity of the extrapolation. The effect of tacticity is reflected also in the glass transition region; the isotactic sample has its T_g about 65°C lower with greater intensity than the syndiotactic polymer.     

Configurational effects on the crystalline morphology and amorphous phase behavior in poly(3‐hydroxybutyrate) blends with tactic poly(methyl methacrylate)

Poly(3‐hydroxybutyrate) (PHB) blends with two tactic poly(methyl methacrylate)s [PMMAs; isotactic poly(methyl methacrylate) (iPMMA) and syndiotactic poly(methyl methacrylate) (sPMMA)], being chiral/tactic polymer pairs, were investigated with regard to their crystalline spherulite patterns, optical birefringence, and amorphous phase behavior with polarized optical microscopy and differential scanning calorimetry. The PHB/sPMMA and PHB/iPMMA blends exhibited upper critical solution temperatures of about 225 and 240°C, respectively, on the basis of the results of thermal analysis and phase morphology. The interactions of two constituents in the blends (PHB/iPMMA or PHB/sPMMA) were measured to be insignificantly different for the PHB/sPMMA and PHB/iPMMA blends. However, syndiotacticity in PMMA exerted a prominent effect on the alteration of the PHB spherulite morphology, whereas, by contrast, isotacticity in PMMA had almost no effect at all. At high sPMMA contents (e.g., 30 wt %) in the PHB/sPMMA blend, the spherulites were all negatively birefringent and ringless when they were crystallized at any crystallization temperature between 50 and 90°C. That is, not only was the original ring‐banded pattern in the neat PHB spherulites completely disrupted, but the optical sign was also reverted completely from positively to negatively birefringent in the sPMMA/PHB blend; this was not observed in the iPMMA/PHB one. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Stereo complexes in solutions of syndio- and isotactic poly(methyl methacrylate) mixtures: 2. Mutual interaction constant of stereo polymers

The coefficient of interaction between syndiotactic and isotactic poly(methyl methacrylate) was determined at 25°C in solutions of a mixture of these two polymers in dioxan and chlorobenzene by using the method of instrinsic viscosity measurement in a ‘polymer solvent’. In these systems where stereocomplexes are formed the coefficient is unusually high and depends on the solvent used.     

Investigation of thermal behavior of poly(2‐hydroxyethyl methacrylate‐co‐itaconic acid) networks

The thermal behavior of poly(2‐hydroxyethyl methacrylate) [PHEMA] homopolymer and poly(2‐hydroxyethyl methacrylate‐co‐itaconic acid) [P(HEMA/IA)] copolymeric networks synthesized using a radiation‐induced polymerization technique was investigated by differential scanning calorimetry, thermogravimetric analysis, and Fourier transform infrared spectroscopy. The glass‐transition temperature (T_g) of the PHEMA homopolymer was found to be 87°C. On the other hand, the T_g of the P(HEMA/IA) networks increased from 88°C to 117°C with an increasing amount of IA in the network system. The thermal degradation reaction mechanism of the P(HEMA/IA) networks was determined to be different from the PHEMA homopolymer, as confirmed by thermogravimetric analysis. It was observed that the initial thermal degradation temperature of these copolymeric networks increased from 271°C to 300°C with IA content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1602–1607, 2007     

Polymerization of allyl methacrylate with nylon 6 using benzoyl peroxide as initiator

Polymerization of allyl methacrylate with nylon 6 using benzoyl peroxide as initiator was carried out under different conditions. The polymer add-on was dependent upon allyl methacrylate and benzoyl peroxide concentrations, polymerization time and temperature as well as addition of metallic salts or organic solvents. The polymer add-on increased by increasing benzoyl peroxide concentration up to 0.5 mmol/l then decreased by further increase in peroxide concentration, whereas it increased as the allyl methacrylate concentration increased from 80 – 300 mmol/l. A polymerization temperature of 85°C constituted the optimal temperature, below or above this temperature resulted in lower polymer add-on. The effect of polymerization time was related to the polymerization temperature, no induction period occured at 95°C in contrast to 15 and 30 minutes at 85°C and 75°C, respectively. The incorporation of Cu^{+ +}ions in the polymerization system improved the magnitude of polymer add-on. A similar situation was encountered with Fe^{+ + +} and Li⁺ ions. Using a water/organic solvent mixture as a polymerization medium was advantageous in enhancing polymer add-on provided that the organic solvent did not exceed 1% in case of ethanol and isopropanol and 4% in case of methanol.     

On the stereochemical composition of poly(vinyl chloride) (PVC) and polypropylene (PP): a phenomenological study

The number of mmr‐ and rrm‐based structures which occur necessarily whenever an isotactic or a syndiotactic sequence breaks off respectively; the extent to which they are isolated or are extended to atactic sequences, and the fact that the mmr repeating sequence, especially when it takes the GTTG^?TT conformation, is shorter and exhibits greater local free volume than rrm, mmm and rrr sequences, are shown to be the stereochemical composition determining structures in poly(vinyl chloride) (PVC) and polypropylene (PP) polymers. These structures, as analyzed by ¹³C NMR spectroscopy and probability calculations, have been determined as a function of the overall tacticity for one series of samples prepared by bulk polymerization at temperatures varying from ?50 °C to 70 °C, and one series of samples prepared by polarity‐based fractionation of a commercial polymer. Using this approach, the stereochemical composition of the samples could be identified. The results are of interest to understand the changes in the physical properties as shown in earlier and current work for both series of polymers. © 2003 Society of Chemical Industry     

Structure and properties of hybrid poly(2‐hydroxyethyl methacrylate)/SiO2 monoliths

Hybrid poly(2‐hydroxyethyl methacrylate) (PHEMA)/SiO₂ monoliths were synthesized via a sol–gel process of the precursor tetraethyl orthosilicate (TEOS) and the in situ free‐radical polymerization of 2‐hydroxyethyl methacrylate (HEMA). The weight ratio of the starting chemicals, TEOS to HEMA, was varied between 100/0 and 0/100. Structural analysis was performed by IR and NMR. The NMR results indicated that the introduction of PHEMA in the silica networks gave rise to a lower degree of condensation of TEOS. The resulting monoliths showed more than 75% transmittance in the visible region, that is, good transparency. Mechanical properties were studied with an Instron tester, and the monoliths exhibited better compressive strength and modulus than did bulk PHEMA. Surprisingly, thermogravimetric analysis (TGA) data showed greater than 50 wt % solid residue up to 700°C, possibly related to some degree of chemical crosslinking between the polymer and the silica moiety, which would greatly improve the thermal stability of such hybrid monoliths compared with a pure PHEMA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3168–3175, 2003     

Structure and morphology of poly(β‐hydroxybutyrate) synthesized by ring‐opening polymerization of racemic (R,S)‐β‐butyrolactone with distannoxane derivatives

Predominantly syndiotactic poly((R,S)‐β‐hydroxybutyrate) (PHB) was synthesized by ring‐opening polymerization of racemic β‐butyrolactone with distannoxane derivatives as catalysts. We have studied the polymerization of (R,S)‐β‐BL using distannoxane derivatives as catalysts and the effects of polymerization time on crude yield and molecular weight of the polymers obtained. Then, a more detailed study of the characterization of polymers obtained using hydroxy‐ and ethoxy‐distannoxanes was performed. ¹³C NMR spectroscopy resolved stereosequences in synthetic PHB at the diad level for the carbonyl carbon and at the triad level for the methylene carbon. These analyses show that distannoxane catalysts produce preferentially syndiotactic polyesters (syndiotactic diads fraction from 0.56 to 0.61). Triad stereosequence distribution of PHB samples agrees favourably with the Bernoullian statistical model of chain‐end control, where ideally Φ = 4(mm) (rr)/(mr + rm)² = 1 for perfect chain‐end control. Polymer samples synthesized from distannoxane catalysts are composed of two distinct transition endotherm components with peak temperatures of approximately 42 °C and 75 °C. The formation of two melting endotherms may be due to the presence of two different crystalline structures. © 2000 Society of Chemical Industry     

The transport phenomena of some model solutes through postcrosslinked poly(2-hydroxyethyl methacrylate) membranes with different tactic precursors

Two series of membranes of various degree of hydration have been prepared by postcrosslinking highly syndiotactic and isotactic poly(2-hydroxyethyl methacrylate) [P(HEMA)] with various amounts of hexamethylene diisocyanate (HMDIC). The equilibrium water content, the partition coefficient, and the permeability of the model solutes such as urea, acetamide, NaCl, 2-propanol, and isobutanol for these membranes were measured. In addition, differential scanning calorimetry (DSC) study for the membranes was performed. The membranes of the isotactic precursor are more hydrated at 25°C compared to the ones of its syndiotactic counterpart. This may be due to the more hydrophobic nature of syndiotactic P(HEMA). The partition coefficient data show that the solutes of urea, acetamide, and NaCl are partitioned only into the water-containing region, whereas the alcohol solutes are preferentially sorbed on to polymer matrix. The permselectivity data of urea to NaCl reveal that the permselectivity of crosslinked isotactic P(HEMA), (ISO) membranes increases as the amount of HMDIC is increased from 2.5 to 10 mol %, while the trend is reversed for crosslinked syndiotactic P(HEMA), (SYN) membranes. The apparent diffusivity order of urea, acetamide, and NaCl is not the same in those two characteristic membranes: the order is urea > NaCl > acetamide for highly crosslinked ISO membranes, and NaCl > urea > acetamide for all SYN membranes, which was compared with the free diffusion data in aqueous solution and interpreted in terms of the water-structural orderlines within membranes.